Surface treated metal oxide polymerization catalyst and method of preparation



United States Patent SURFACE TREATED METAL OXIDE POLYMERIZA- TIONCATALYST AND METHOD OF PREPARA- TION Adam Orzechowski, Waltham, andJames C. MacKenzie, Wellesley Hills, Mass, assignors to CabotCorporation, Boston, Mass., a corporation of Delaware N0 Drawing. FiledSept. 30, 1963, Ser. No. 312,334

19 Claims. (Cl. 252-429) This application is a continuation-in-part ofapplication Serial No. 15,815, filed March 18, 1960, by Adam Orzechowskiand James C. MacKenzie, and now abandoned.

This invention relates to novel polymerization catalysts and catalystcomponents and to a process for producing polymerization catalystcomponents.

In a copending application, Serial No. 300,049, filed August 5, 1963, byYancey and MacKenzie, which application is a continuation in part ofSerial No. 197,231, filed May 24, 1962, and now abandoned, there isdisclosed a process for producing novel ion exchange materials byreacting an alkali metal or certain alkali metal compounds with hydroxylgroups on the surface of certain inorganic oxides.

It has also been disclosed, for example, in the aforementioned copendingUS. patent application of Adam Orzechowski and James C. MacKenzie thatinorganic solids bearing chemically combined on the surface there? of,surface structures comprising IIIX IIIX X e a e X X X X X X wherein Z isa metal of period 4 of Group VIII; each X is any halogen and whereinsaid structures are chemically linked directly from Z to at least oneoxygen atom in the surface of said inorganic solid comprise superiorcatalyst components which, when combined with suitable organometalliccompounds produce superior polymerization catalysts.

In accordance with said patent application of Orzechowski and MacKenzie,said catalyst components are produced by reacting a metal halide oroxyhalide of period 4 of Group VIII (hereinafter for the sake of brevitycollectively referred to as Group VIII halides) with hydroxyl groups onthe surface of a finely-divided inorganic solid as is illustrated in thefollowing equation in which ferric chloride represents the Group VIIIhalides, and silica represents the inorganic solid bearing hydroxylgroups on the surface thereof:

EQUATION 1 Si Si o o si on FeCl; SiO-FeClz H01 0 0 Si Si In said methodof making said catalyst components,

the gaseous by-product of the above reaction, i.e. hydrogen halide,should be removed from the reaction medium in order to produce acatalyst component of reproducible character and performance. Secondly,the kinetics of the above reaction are such that considerable time andheat energy are normally required in the efiicient formation of saidcatalyst component. In accordanw with the present invention, however,by-products which need be removed are often not produced and formationof said catalyst components is normally more readily achieved.

ice

Accordingly, it is a principal object of the present invention toprovide novel catalysts.

It is another object of the present invention to provide an improvedprocess for producing novel catalyst components.

Other objects of the present invention will in part be obvious and willin part appear hereinafter.

It has been discovered that said catalyst components are produced in arelatively short time by reacting (a) catalyst component intermediatescomprising a reaction product of the type produced by reacting, asdisclosed in detail in US. Serial No. 300,049, hydroxy groups on thesurface of a finely-divided inorganic solid and an alkali metal orcertain alkali metal compounds with (b) a Group VIII halide.

Inorganic solids suitable for the purposes of the present inventiongenerally include any relatively inert solid having at least about 1X10and preferably at least about 5 l0 equivalent per gram of hydroxylgroups on the surface thereof and an average particle diameter of lessthan about 0.1, and preferably less than about 0.05 micron. For example,metal oxides such as titania, zirconia, thoria, magnesia and silica,silicates such as chrysotile, actinolite and crocidolite, and aluminatessuch as corundum and bauxite are all generally suitable for the purposesof the present invention provided the surface hydroxyl groupconcentration and the particle size are appropriate.

It is pointed out, however, that the alkali metals and alkali metalcompounds of the present invention are relatively strong reducingagents. Accordingly, when an inorganic solid is utilized which isreducible, for example, titanium dioxide, it is extremely important thatthe quantity of alkali metal or alkali metal compound reacted therewithnot exceed that quantity stoichiometrically necessary to react with allthe hydroxyl groups on the surface of the solid. While saidstoichiometric quantity should not be exceeded even when a non-reducibleinorganic solid is utilized it is particularly important, for obviousreasons, to avoid an excess when a reducible solid is utilized. On theother hand, it is generally desirable to add no less than saidstoichiometric quantity as any hydroxyl groups left unreacted cansubsequently detrimentally affect the performance of the catalyst formedby combining the catalyst component produced with an organometalliccompound.

The alkali metals, by which is meant lithium, sodium,

potassium, rubidium, cesium and francium, in metallic form are allgenerally suitable for the purposes of the present invention. Inaddition, alkali metal compounds conforming to the empirical formulawherein M is an alkali metal and R is chosen from the group consistingof any monovalent hydrocarbon and hydrogen are suitable for the purposesof the present invention.

Specific examples of R groups for substitution in the above formulainclude methyl, ethyl, n-propyl, isobutyl, n-amyl, isoamyl, hexyl,n-octyl, n-dodecyl, and the like; 2-butenyl, 2-methyl-2-butenyl, and thelike; cyclopentylmethyl; cyclohexylethyl, cyclopentylethyl,methylcyclopentylethyl, 4-cyclohexenylethyl and the like; Z-phenylethyl,a-naphthylethyl, methylnaphthylethyl, and the like; cyclopentyl,cyclohexyl, 2,2,l-bicycloheptyl, and the like; rnethylcyclopentyl,dimethylcyclopentyl, ethylcyclopentyl, methylcyclohexyl,dimethylcyclohexyl, ethylcyclohexyl, isopropylcyclohexyl,S-cyclopentadienyl, and the like; phenylcyclopentyl, phenylcyclohexyl,and the corresponding naphthyl derivatives of cycloalkyl groups, and thelike; phenyl, tolyl, xylyl, ethylphenyl, xenyl, naphthyl, methyl- 3naphthyl, dimethylnaphthyl, ethylnaphthyl, and cyclohexylphenyl.

Examples of compounds conforming to the above formula, and which aretherefore suitable for the purposes of the present invention, areethyllithium, hexyllithium, cyclopentadienylsodium, octylpotassium,butyllithium, sodium hydride, cesium hydride and rubidium hydride.Moreover, complexed compounds which conform to the above empiricalformula, such as diphenyldilithiurn and diphenylpotassium lithium arealso generally suitable for the purposes of the present invention.

The conditions under which reaction between the alkali metal or alkalimetal compound and hydroxyl groups on the surface of the finely-dividedsolid can be accomplished in order to produce a catalyst componentintermediate are subject to considerable variation. However, in order toobtain a catalyst component intermediate with reproducible character andperformance, it has been found to be all important that thefinely-divided solid be essentially dry and anhydrous (i.e., free ofmolecular water in any form) at the time it is brought into contact withthe alkali metal or alkali metal compound. When the finely-divided solidto be utilized contains molecular water in any form and/ or tends toabsorb same on exposure to humid atmospheres, etc., it must be driedimmediately before use, or after drying must be maintained continuouslyout of contact with water vapor until utilized. If the precaution ofusing a substantially anhydrous finely-divided solid is not observed,the desired chemical reaction either does not occur at all or does notpredominate to the extent necessary to produce a superior catalystcomponent intermediate. Instead, products are obtained which are veryinferior as catalyst component intermediates in that the concentrationof alkali metal present on the surface of the particulate solid isreduced due to reaction of the alkali metal or alkali metal compoundwith moisture.

In the case of the alkali metal compounds conforming to the formula M"R,the reaction is preferably accomplished by contacting the finely-dividedsolid with a solution or a good dispersion of the alkali metal compoundin an inert hydrocarbon reaction medium, and maintaining the tworeactants in intimate contact for a period of time sufficient to efiFectthe desired metathetical chemical reaction resulting in the chemicalbonding of the alkali metal to the finely-divided solid. The length oftime required to effect a given amount of such reaction and chemicalbonding is largely dependent upon the temperature.

Generally speaking, any temperature between about C. and about 125 C.can be used satisfactorily,

but room temperature or higher will generally be used. Assumingprovision is made for intimate contact of the dry, finely-divided solidand the alkali metal compound, the minimum time required to accomplishthe chemical reaction needed will vary to some extent with thetemperture utilized, i.e., the higher the temperature utilized, theshorter the reaction time required. Temperatures substantially higherthan about 125 C., e.g., 150-175" C., often cause the decomposition ofalkali metal compounds and moreover are completely needless, andtherefore of little or no interest.

Various classes of hydrocarbons or their mixtures which are liquid andsubstantially inert under the reaction conditions of the present processconstitute suitable liquid reaction media. Thus, various classes ofsaturated hydrocarbons such as pure alkanes, cycloalkanes andcommercially available mixtures, freed of harmful impurities, aresuitable for the purposes of the present invention. For example,straight run naphthas and kerosenes, liquefied alkanes, aromatichydrocarbons, and particularly the mononuclear aromatic hydrocarbonssuch as benzene, toluene, xylenes, mesitylene, and xylenep-cymenemixtures and the like are all completely suitable. Also, ether-typesolvents, such as 1,2-dimcthoxyethane, and tetrahydrofuran dioxane areuseful particularly in cases where the alkali metal compound isinsoluble in a true hydrocarbon solvent. Thus, for the purposes of thepresent invention, ether-type solvents are included within the scope ofthe term, hydrocarbon solvents.

Although use of the alkali metal compounds in liquid or solution formgenerally gives excellent results, the reaction of the alkali metalcompound with hydroxyl groups on the surface of the finely-divided solidcan also be effected if the latter is exposed to sufiicient quantitlesof the vapors of an alkali metal compound under conditions of time andtemperature similar to those discussed above. The vapors of many alkalimetal compounds can be supplied under their own vapor pressure using apartial vacuum if necessary, or with the aid of a dry, inert carrier gassuch as nitrogen. Said vapor phase treatment can be accomplished in anysuitable manner such as by circulating the vapors through theparticulate solid in a fixed, moving or fluidized bed reactor.

In the case of the alkali metals in metallic form however, reaction withhydroxyl groups on the surface of the finely-divided solid in ahydrocarbon solution is not generally feasible due to the very lowsolubility of the alkali metals in most hydrocarbon media. On the otherhand, reaction of alkali metal vapors with the finelydivided solid isnot generally practicable due to the extremely low volatility of thealkali metals. The reactions of alkali metals with the finely-dividedsolid can, however, be accomplished by reacting in an inent hydrocarbonmedium (as specified above) a finely-divided solid and finely comminutedalkali metal. Briefly, a suitable procedure for accomplishing saidreaction comprises placing a finely-divided solid and an alkali metal ina hydrocarbon solvent having a boiling point higher than the meltingpoint of the alkali metal, melting the alkali metal by heating thehydrocarbon medium to a temperature above the melting point of thealkali metal but preferably below the boiling point of the hydrocarbonmedium, and subsequently comminuting the molten alkali metal, forexample, by stirring the hydrocarbon medium with a high speed stirrer.Under these conditions, the alkali metal will react with the hydroxylgroups on the surface of the solid.

The accomplishment of an actual chemical reaction of controlled extentbetween hydroxyl groups on the surface of the finely-divided solid andthe alkali metals or alkali metal compounds is of utmost importance inobtaining catalyst component intermediates of reproducible character andperformance because the ultimate caltalystic activity of a catalystcomponent is generally highly dependent upon the amount of alkali metalchemically combined to the surface of a given weight of thefinely-divided solid. Accordingly, in preparing the surface reactedfinely-divided solids of the present invention, it should be kept inmind that the smaller the average particle size of the solid and thelarger the quantity of hydroxyl groups on the surface thereof, thegreater will be the potential activity and efficiency of the catalystcomponent producible therefrom. Therefore, it is important to use as thestarting material particulate, finelydivided solids having an averageparticle diameter of less than about 0.1 micron, and ideally less thanabout 0.05 micron, and having a hydroxyl group concentration on thesurface thereof of at least about 1 l0 and preferably at least about 510- equivalents per gram of solid.

Although the mechanism of the reaction between the alkali metals oralkali metal compounds and the solid is not completely understood, it isknown that the alkali metals and alkali metal compounds react with thehydroxyl groups on the surface of the solid liberating byproducts suchas the corresponding alkane when an alkali metal alkyl is utilized, orhydrogen when an alkali metal or an alkali metal hydride is utilized. Itis believed, although there is no intent to be bound by thisexplanation, that the reactions which occur are of the type illustratedby the following equations, wherein silica serves as the finely-dividedsolid and sodium metal, sodium hydride and lithiumbutyl, respectively,serve as the alkali metal reactants:

EQUATION 2 Si-OH Na Si-ONa %Hg metal O O EQUATION 3 0 0 Si-OH N 'aHSiONa H:

EQUATION 4 O O Si -OE LiCiHs SiOLi C4Hi0 When said alkali metallatedsolids are reacted with a Group VIII halide, catalyst components of thetype disclosed in US. patent application Serial No. 15,815 are produced.I

Group VIII halides and oxyhalides are generally suitable for thepurposes of the present invention. Examples of suitable compounds areferric chloride, cobaltous chloride, nickelous chloride, cobaltousbromide, ferric bromide, ferrous chloride and ferrous bromide.

The conditions under which reaction between the Group VIII halides andthe finely-divided, alkali metallated solids can be accomplished aresubject to considerable variation. However, as has been previouslystated with regard to the formation of the alkali metallated solids, inorder to obtain a catalyst component with exceptionally high activity,and reproducible character and performance, it has been found to be allimportant that the finely-divided alkali metallated solid be maintainedessentially dry and anhydrous (i.e. free of molecular water in any form)prior to as well as at the time it is brought into contact with theGroup VIII halides. Generally, the said reaction can be carried out bycontacting said alkali metallated solid with said Group VIII halides,preferably in a solution thereof in an inert hydrocarbon medium, andmaintaining the two reactants in intimate contact for a period of timesufficient to effect the desired chemical reaction resulting in thechemical bonding of the Group VIII metal to the solid. The length oftime required to effect a given amount of such reaction and chemicalbonding is largely dependent upon the temperature of the reactionmixture. Generally speaking, almost any temperature between about C. andabout 200 C., and even higher temperatures can be used satisfactorily,but room temperature to about 100 C. is generally preferred. Assumingprovision is made for intimate contact of the alkali metallated solidand the Group VIII halides, the minimum time required to accomplish thechemical reaction will vary from periods of about one hour at about roomtemperature to periods of about five minutes at temperatures of 100 C.or over. Temperatures substantially higher than about 200 C., e.g. 500C., are completely needless and therefore of little or no interest.

It is believed that the type of reaction that occurs is correctlyillustrated by the following illustrative equation, wherein silicabearing chemically bound lithium 6 on the surface thereof serves as thealkali metallated solid and ferric chloride serves as the Group VIIIhalide:

EQUATION s SiOLi+FeCl SiOFeCl +LiCl Also, it is pointed out that inorder to obtain a catalyst component of the highest possible activity,aside from observing the above important precautions and reactionconditions, it is also recommended that the quantity of Group VIIIhalide with which the solid is contacted be at least approximatelysufficient to provide one atom of Group VIII metal for each three atomsof alkali metal on the surface of the inorganic solid, in order topromote reaction with as many of the alkali metal sites as possible,since any sites left unreacted might tend to aifect the performance ofthe catalyst which will be subsequently produced.

Moreover, it is generally desirable to use somewhat more than thisminimum amount of Group VIII halide and to restrict the reactiontemperature in order to favor the reaction illustrated. by Equation 6,rather than that illustrated by Equation 8, which follow, because theproducts of Equation 6 are generally more active as catalyst componentsthan are the products of Equation 7 whereas the products of Equation 8are normally inactive as polymerization catalyst components in theprocesses encompassed by the present invention.

EQUATION 6 0 o Si O Li e1 0 Li 0 o SiOLi+ reoi, SiOFeClz+ LiCl o o Si OLi si o Li 0 o EQUATION 7 o o si oLi SiOLi o 0 Si0 Li Feel, si o o 0FeO1 2Li0l si om Si O o 0 EQUATION 8 \O Si O Li si o o o si OLi FeonSiO-Fe 31.101

0 o SiOLi Si0 o o On the other hand, if more Group VIII halide isintroduced than will react, the excess is preferably removed beforeformation of the catalyst. Although the excess can be removed byextraction, it is obviously more desirable to avoid such additionalsteps.

In order to form the catalyst of the present invention, the cocatalystis combined with a suitable organometallic compound. Suitableorganometallic compounds are any of the compounds conforming to thegeneral formula:

MM X R wherein M is a metal chosen from Groups I, II and III of theperiodic table; M is a metal of Group I of the periodic table; v is anumber from to l;'each X is a halogen; n is a number from Oto 3; each Ris any monovalent hydrocarbon radical or hydrogen; and y is a numberfrom 1 to 4.

Compounds of a single Group I, II or III metal which are suitable forthe .practice of the invention include compounds conforming to thesubgeneric formula:

wherein M is a Group I, II or III metal, such as lithium, sodium,beryllium, barium, boron, aluminum, copper, zinc, cadmium, mercury andgallium; wherein k equals 1, 2 or 3 depending upon the valency of Mwhich valency in turn normally depends upon the particular group (i.e.I, nor III) "to which M belongs; and wherein each R may be anymonovalent hydrocarbon radical. Examples of suitable R groups includeany of the R groups aforementioned in connection with the formula Thus,entirely suitable for the purposes of the present invention are theorganocompounds of Groups I,- II and III, such as methyl andbutyllithium, pentenylsodium, dihexylmercury, diallylmagnesium,diethylcadmium, benzylpotassium, di-p-tolylmercury, diethylzinc,tri-n-butylaluminum, methyl phenylmercury, diisobutylethylboron,diethylcadmium, d-in-butylzinc and tri-n-amylboron, and in particularthe aluminum alkyls, such as trihexylaluminum, triethylaluminum,trimethylaluminum, and in particular triisobutylaluminurn.

In addition, mono-organo-halides and hydrides of Group II metals, andmonoor di-organo-halides and bydrides of Group III metals conforming tothe above general formula are also suitable. Specific examples of suchcompounds are diisobutylaluminum bromide, isobutylboron dichloride,methylmagnesium chloride, phenylmercuric iodide, ethylberylliumchloride, ethylcalcium bromide, hexylcupric chloride, diisobutylaluminumhydride, methylcadmium hydride, diethylboron hydride, hexylberylliumhydride, dipropylboron hydride, octylmagnesium hydride, butylzinchydride, dichloroboron hydride, dibromoaluminum hydride and bromocadmiumhydride.

Also, compounds comprising a Group I, II or III metal compound complexedwith a Group I metal compound if they conform to the above generalformula, are generally suitable. Examples of such compounds aretetraethyllithium aluminum, tetrahexyllithium aluminum,trihexylpotassium aluminumchloride, triethyllithium aluminum bromide,tributylsodium zinc, tributyllithium zinc, trioctadecylpotassiumaluminum hydride, diphenyldilithium and diphenylpotassium lithium.

Although it is appreciated that when R, in the above defined generalformula, does not comprise at least one hydrocarbon radical, the GroupI, II, and III metal compounds of the present invention cannot normallybe termed organometallic compounds, compounds lacking at least onehydrocarbon radical comprise such a relatively small number of the totalnumber of compounds included by said general formula that for thepurposes of the present invention, it is intended that these compoundsbe included Within the generic term, organometallic compound.Accordingly, in the specification and in the claims, it is intended, andtherefore it should be understood, that the term, organometalliccompound, refers to all the compounds included within the scope of theabove defined general formula.

Using the catalysts of this invention, polymerization of the olefiniccharging stock can be accomplished in the absence of liquids, solventsor diluents, for example, in the gas phase, but it is usually desirableto effect polymerization in the presence of the subtsantially inertliquid reaction medium which functions as partial solvent for themonomer, a solvent for the organometallic compound, as a heat transferagent, and/or as a liquid transport medium to remove normally solidpolymerization products as a dispersion from the polymerization reactor,thus permitting efficient and continuous polymerization operations.

Accordingly, in inert liquid reaction medium is preferably supplied onthe reaction zone.

Several classes of hydrocarbons or their mixtures which are liquid andsubstantially inert under the polymerization conditions of the presentprocess constitute suitable liquid reaction media. Obviously, these samehydrocarbon media are normally suitable for use where heretofore the useof a hydrocarbon medium has been suggested or is considered desirable.Thus, various classes of saturated hydrocarbons such as pure alkanes orcycloralkanes or commercially available mixtures, freed of harmfulimpurities, are suitable for the purposes of the present invention. Forexample, straight run naphthas or kerosenes containing alklanes andcycloalkanes and liquid or liquefied alkanes such as propane, butanes,npentane, n-hexane, 2-3-dimethylbutane, n-octane, isooctane,2,2,4-trimethylpent-ane, n-decane, n-dodecane, cyclohexane, methylcyclohexane, dimethylcyclopentane, ethylcyclohexane, decalin,methyldecalin, dimethyldecalins and the like are suitable. Also, membersof the aromatic hydrocarbon series, such as ethylbenzene,isopropylbenzene, sec-butylbenzene, t-butylbenz-ene, ethyltoluene,ethylxylenes, hemimellitene, pseudocumene, isodurene, d'iethyl benzene,isoamylbenzene, and particularly the mononuclear aromatic hydrocarbonssuch as benzene, toluene, xylenes, mesitylene and xylene-p-cymenemixtures, and the like are completely suitable. Aromatic hydrocarbonfractions obtained by the selective extraction of aromatic naphthas,from hydroforming operations such as distillates or bottoms, from cyclestock fractions or cracking operations, etc., and certain alkylnaphthalenes which are liquid under the polymerization reactionconditions, for example, l-methylnaphthalene, 2-isopropylnaphthalene,l-n-amylnaphthalene and the like, or commercially produced fractionscontaining these hydrocarbons and the like are also suitable.

The proportion of surface reacted particulate inorganic solid toorganometallic compound utilized in preparing the catalyst is notusually a critical feature of the process. Moreover, if this proportionis expressed as a simple molar or weight ratio, it may not beparticularly meaningful because, as indicated above, the efliciency ofsaid surface reacted solids (on a weight or molar basis) is highlydependent upon the proportion of Group VIII halide chemically combinedtherewith. Accordingly, in order to be most meaningful the relationshipbetween catalyst components should be expressed as a function of theamount of Group VIII halide which has reacted with the surface of thefinely-divided solid. We have found from experience that a molar ratioof from 0.1 to 3 millimoles of the organometallic compound per milliatomof Group VIII metal chemically combined with the surface of thefinely-divided solid is to be preferred.

The quantity of catalyst i.e., comprising both the surface reactedfinely-divided solid and the organometallic compound, to be utilized inthe polymerization reaction may vary, the precise proportion relative tothe amount of monomers used being selected in accordance with the rateof polymerization desired, the geometry of the reaction zone, thecomposition of the particular olefinic charging stock, temperature andother reaction variables. It should be pointed out that in general theefiiciency of the catalysts of the present invention is extremely highand accordingly, the total quantity of catalyst that need be employedbased on the weight of the charging stock is very small particularlywhen a very fine particle size oxide is utilized as the inorganic solid.

Harmful impurities in the liquid hydrocarbon reaction medium can beeffectively neutralized prior to the formation therein, or additionthereto, of the catalyst or catalyst components by treating the liquidmedium with a metal alkyl. The olefinic charging stocks can be purifiedby any known means such as bubbling said stocks through a solution of ametal alkyl in a hydrocarbon solvent prior to the introduction into thepolymerization reactor.

Temperature control during the course of the polymerization process canbe readily accomplished when a liquid hydrocarbon diluent is utilizedbecause of the presence in the reaction zone of a large liquid masshaving relatively high heat capacity. The liquid hydrocarbon reactionmedium can be cooled by heat exchange inside or outside the reactionzone.

The contact time or space velocity employed in the polymerizationprocess will be selected with reference to the other process variablessuch as the particular catalysts utilized, the specific type of productdesired, and the extent of olefin conversion desired in any given run orpass over the catalyst. In general, this variable is readily adjustableto obtain the desired results.

There follows a number of illustrative non-limiting examples:

Example 1 To a 2000 milliliter, three neck, glass reaction vesselequipped with a stirrer and condenser, there is added 20 grams ofCab-O-Sil, a pyrogenic silica produced by Cabot Corporation, which hasan average particle diameter of about 10 millimicrons and a hydroxylgroup content on the surface thereof of about 1.5 milliequivalents/ gramand 1450 milliliters commercial grade n-heptane. The resulting slurry'is then continuously stirred and azeotropically dried for a period of'24 hours during which time about 450 milliliters of -a water/n-heptaneazeotrope are distilled from the vessel. Next, there is added to saidvessel about 25 millimoles of butyllithi-um dissolved in 250 millilitersanhydrous n-heptane. The vessel is then continuously stirred at ambienttemperature for a period of 20 minutes. Subsequently, the extent of thereaction between the butyllithium and hydroxyl groups on the surface ofthe silica is determined by analyzing the liquid contents of the vesselto insure the absence therein of butyllithium, and the said silica isfound to have about 25 milliequivalents of lithium chemically bound tothe surface thereof. Next, about 20 millimoles of ferric chloride in 250milliliters of anhydrous n-hept-ane is added to the alkali metallatedsilica slurry with continuous stirring at about 65 C. After about 1.5hours the extent of the reaction between the ferric trichloride and thealkali metallated silica is determined by testing the liquid contents ofthe vessel for the absence therein of ferric trichloride and byanalyzing the solid contents of the vessel for lithium chloride and thesaid silica is found to have 20 milliatoms of iron chemically bound tothe surface thereof. 150 milliliters of this slurry containing about 2grams of silica to which there is chemically bound about 2 milliatoms ofiron is then transferred from this reaction vessel to a one-gallonstainless steel autoclave, equipped with a stirrer and pre viouslyflushed with dry nitrogen. Next, about 1500 milliliters of anhydrousn-heptane and about 5 millimoles triethylaluminum are introduced intosaid autoclave and the autoclave is then continuously agitated andheated to, and maintained at, about 95 C. After about five minutes,ethylene gas is introduced into said vessel to a total pressure of about500 p.s.i.g. and said pressure is then maintained for about 2 hours bythe periodic introduction, as needed, of additional ethylene gas. Uponexamination of the products of the reaction, it is found that about 15grams of polyethylene has been produced.

Example 2 This example is essentially a duplicate of Example 1, with theexception that in this example azeotropic distillation of thesilica/commercial grade n-heptane slurry 10 is not carried out. 20minutes after the addition of the ferric chloride as described inExample 1, the silica is analyzed and it is found that there is no ironchemically bound to the surface thereof.

Obviously, many changes can be made in the above description, examplesand procedures without departing from the scope of the presentinvention. Thus, for example, the catalyst components of the presentinvention instead of being treated with an organometallic compound suchas triethylaluminum as in Example 1, can be subjected to ultravioletradiation or reacted with a silane such as .trimet-hoxysilane-(CH O) SiHin order to produce products useful as catalyst for polymerization. Alsofor example, although only ferric chloride is mentioned in the aboveexamples, other Group VIII halides as set forth above in detail are alsosuitable.

Also, although only an alkali metal alkyl is specifically mentioned inthe above examples, alkali metals and alkali metal hydrides (i.e.lithium hydride, potassium hydride, cesium hydride, etc.) are alsosuitable for the purposes of the present invention.

Also, pyrogenically coformed, or coprecipitated metal oxides, or metaloxides coformed with, or mixed with, other compounds are suitable forthe purposes of the present invention, although pyrogenically formed andcoformed oxides are definitely preferred.

Accordingly, it is intended that the above disclosure be regarded asillustrative and as in no Way limiting the scope of the invention.

What we claim is:

1. A process for producing a polymerization catalyst component whichcomprises reacting (a) a finely-divided metal oxide having an averageparticle diameter of less than about 0.1 micron and bearing in chemicalcombination on the surface thereof at least about l 10 gram atoms pergram of alkali metal which is chemically bonded directly to an oxygenatom in the surface of said oxide, with (b) a halide of a metal ofperiod 4 of Group VIII.

2. The process of claim 1 wherein said alkali metal chemically bound tothe surface of said oxide is lithium.

3. The process of claim 1 wherein said alkali metal chemically bound tothe surface of said oxide is sodium.

4. The process of claim 1 wherein said alkali metal chemically bound tothe surface of said oxide is potasslum.

5. The process of claim 1 wherein said oxide is chosen from the groupconsisting of alumina and silica.

6. The process of claim 1 wherein said oxide is chosen from the groupconsisting of alumina and silica having an average particle diameter ofless than about 0.05 micron and wherein said oxide has chemically boundthereto at least about 5 10- gram atoms per gram of an alkali metal.

7. The process of claim 1 wherein said Group VIII halide is an ironhalide.

8. The process of claim 1 wherein said Group VIII halide is an ironchloride.

9. The process of claim 1 wherein said Group VIII halide is a ferricchloride.

10. The process of claim 1 wherein said Group VIII halide is a cobalthalide.

11. The process of claim 1 wherein said Group VIII halide is a nickelhalide.

12. A process for producing a polymerization catalyst which comprisesreacting (a) a finely'divided metal oxide having an average particlediameter of less than about 0.1 micron and bearing in chemicalcombination on the surface thereof at least about 1X10- gram atoms pergram of alkali metal which is chemically linked directly to an oxygenatom in the surface of said oxide, with (b) a halide of a metal ofperiod 4 of Group VIII and subsequently combining the resulting oxidehaving Group VIII metal bound thereto with a compound conforming to thegeneral formula:

M is aluminum, v is 0, n is O and each R is any alkyl group.

14. The process of claim 12 wherein said oxide is chosen from the groupconsisting of silica and alumina. 15. The process of claim 12 whereinsaid Group VIII metal bound to said oxide is iron. 16. A catalyst whichcomprises (a) a finely-divided metal oxide having an average particlediameter of less than about 0.1 micron'and carrying in chemicalcombination at least about 1 l0- equivalents per gram of a halide of ametal of period 4 of Group VIII which halide is chemically bondeddirectly to at least one oxygen atom in the surface of said oxide, and(b) a compound conforming to the general formula:

5 wherein M is chosen from the group consisting of the metals of GroupsI, II and III; M is a metal of Group I; v is a number from 0 to 1'; eachX is any halogen; n is a number from 0 to 3; each R is 10 chosen fromthe group consisting of any monovalent hydrocarbon radical and hydrogen;and y is a mum'- ber from l to 4. I 17. The catalyst of claim 16 whereinsaid halide of a metal of period 4 of Group VIII is a chloride. 1 18.The catalyst of 'claim 16 wherein said halide of a metal of period 4 ofGroup VIII is an ironhalide.

19. The catalyst of claim 16 wherein said halide of a metal of period 4of Group VIII is a cobalt halide.

References Cited by the Examiner TOBIAS E. LEVOW, Primary Examiner.

12. A PROCESS FOR PRODUCING A POLYMERIZATION CATALYST WHICH COMPRISESREACTING (A) A FINELY-DIVIDED METAL OXIDE HAVING AN AVERAGE PARTICLEDIAMETER OF LESS THAN ABOUT 0.1 MICRON AND BEARING IN CHEMICALCOMBINATION ON THE SURFACE THEREOF AT LEAST ABOUT 1X10**-4 GRAM ATOOMSPER GRAM OF ALKALI METAL WHICH IS CHEMICALLY LINKED DIRECTLY TO ANOXYGEN ATOM IN THE SURFACE OF SAID OXIDE, WITH (B) A HALIDE OF A METALOF PERIOD 4 OF GROUP VIII AND SUBSEQUENTLY COMBINING THE RESULTING OXIDEHAVING GROUP VIII METAL BOUND THERETO WITH A COMPOUND CONFORMING TO THEGENERAL FORMULA: